Polymethine dyes for synthetic fibers



POLYMETHINE DYES FOR SYNTHETIC FIBERS Nicholas J. Kartinos, Chicago, Ill., and James B. Normington, Belvidere, N. 1., assignors to General Aniline &;Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 11, 1953, Serial No. 397,773

This-i11vention= relates to pelymethine dyes and particularly' to an improved class of i such dyes having eX-" cellent fastnessno. light; washing, high-tinctorial strength and otheruseful properties;

We have found that condensing a substituted p,p -im inodiaryl dialdehyde with a compound containing an active methylene group in the presence of a basic or acid condensing agent yield dyes which are not only of high tinctor-ialstrength and of excellent light and wash-fastness, excellentsublimation properties, but also because of their--brilliance and/or fluorescence are adaptable as fluorescent pigments and as brightening agents. The polymethine dyes are par: tieularlyg adaptable for dyeing" the currently available synthetic fibers, such as, acetate; nylon, Dacron (polyester fiberfrom terephthalic acid andethyle'ne. glycol) and Dynel (copolymer of acrylonitrile and vinyl chloride) to which they impart fluorescent green-yellow shades of excellent light and wash fastnesszand display exceptionally high tinctorial strength.

These polymethine dyes are characterized by the fol lowing generalcformulae:

wherein-R' representsa lower alkyl; e. g., methyl, ethyl, propyl, butyl,- isobutyl,.etc., a ph'enylradical, or a- R1 represents acetyl, cyanoor carbalkoxy, e. ,g., carbo: methoxy, carbethoxy, carbopropoxy, carbobutoxy, etc., R2 represents a benzylor a carbalkoxy group of the'same value as in Rr, acetyl, carbamide, N-alkyl-carba-rnide, i. e., N-methyl-, N-ethyl-, N-propyl-, and-N-butyl-carbamide, etc., N,N-dialkyl-carbamide, i. e., N,Ndimethyl-, N,N- diethyl-, N,N-dipropyl-, and. N,N-dibutyl +carbamide etc., N-hydroxyalkyl-carbamide, e. g.-; N-hydrQXyethyl.-, N- hydroxypropyl-, and N-hydroXybutyl-carbamide," carbochlo-roethoxy, carbohydroxyethoxy, cyanocarbethoxy, p

polymethine dyes obtained by atenf l tolylsulfone and tetrahydrofurfuryl group, R3 represents I either carboethoxy, carboxy, or methyl, and R4 represents 2,766,233 Patented Got. 9,. 1 956 2 either hydrogen, phenyl':Orr-substituted;phenyl, e: g., o

chloro; -m.-sulfonamidosphenyl i and I the like;

In preparing:v the: polymethine: dyescharacterized by the eforegoing formula-a substituted 1p,p.-iminodiarylZ.di-'= aldehyde: is' condensed? with". an active methylene com-- pound in the presence of an acid or basioca-talyst with"- or without a solvent. A basic:.catalyst, however, is pre ferred, such as forexample,alkalinealkoxide, alkaline, such. as, hydroxides, carbonate, and any, of a .variety. of primary;- secondary or tertiary amines.normallypsed'in condensation reactions of thistypet, tertiaryor secondary amines, such as, piperidine, morpho:

line, pyridine, quinolihe, tetrahydroquinoline and the. likemay be employed; A. neutral 5- organictsolvent, .whether.

polar or non-polar and non-interfering in the condensation reaction may be employed if desired. Such solvents constitute-- isopropanol, chloroform; ethanol, methanol, chlorobenzene; As-examples of substituted p,p'-iminodiaryl dialdehydes which..are employed in the foregoing condensation, the -following may be mentioned as being illustrative.

N-methyl-p,p-iminodibenzaldehyde N-ethyl-p,p-iminodibenzaldehyde N-propyl-p,p'-iminodibenzaldehyde N-butylp,p'-iminodibenzaldehyde N-phenyl-ppfiminodibenzaldehyde;

In: addition to. the foregoing: dial-dehydes, compounds obtained; by reacting :aatertiaryrlamine having :two' to three benzene rings 1 attacl1jed.-=to.-the .amino nitrogen withl'a lower dialkyl: formarm'de:v according. to the; processkdescribed in U. S. P. 2,558,285,,may be employed. In place of the specific amines disposed in that patent, the following may be used in like manner to yield the dialdehydes useful for the purpose :of the present invention: N methyldiphenylamine, N,3 dimethyldiphenylamine, N,3,3-trimethyldiphenylamine,. N methyl-3-methoxydi=. phenylamine, Methyl-13,3'=dimetlroxydiphenylamine; N propyl' 3' methyl-3 '-in,eth'oxydiph'enylamine, N'-- butyl'-3'-' chlorodiph'enylamine'," N butyl"- 3,3 dichlorodiphenyl-' amine, N=ethyl-'3'-methyl-3chloroditahenylamine; N-ethyl 3-chloro-3-methoxydiphenylamine, N methyl-3 hydroxy diphenylamine, N-ethyl-3,3,i-dihydroxydiphenylamine, N- ethyl-3-hydroxy-3'-methyldiphenylamine, N-propyl-3-hydroxy-3-chlorodiphenylamine, N-phenyl 3 hydrox -3- ethoxydiphenylamine, N;3',5=trimethyldiphenylamine and others of thesse various isomers.

As regards-examples of compounds containing an active-methylene group'any type of :compound can be=employed fprovided' it "contains- :such a group. and condenses withtan aldehyde by :splitting otfiwithwaten with the resultingformatiom ofa carbon-carbon: double bond. Suitable compounds of this type are for: examplez d rivatives of cyanoaceticacid, such as their esters and amides, derivatives of malonic acid such as malonitrile, malonicesters, andthe like, pyrazolones, dimethyl dihydroresorcinohindolines, oxindoles and-the like. Acetoacetic esters, acetoacetam'ides, benz-yl cyanides and thelike are also included in this.class of compounds.

The following aremore specific examples ofsuch active methylene compounds: ethyl cyanoacetate', cyanoethyl' cyanoacetate, hydroxethyl cyanoacetate; chloroethyl' cy? anoacetate, tetrahydrofurfuryl .cyanoacetate', die'th'yl' mal: onate, dicyanoethyl" malonate," cyanoethyl' hydroxethyl. malonate, cyanoethyl ethyLmalonate, cyanoethylchldro-' ethyl malonate, malonitrile, ethylecetoaoetate, acetoacetamide, cyanoacetamide, N-ethyl ,cyanoacetamide, N,N- diethyl cyanoacetamide, ;N-hydroxyethyl'-cyanoacetamide, l-phenyL-B-methyl 5. pyrazolone, l-ph'enylL-3-carboxy-5- pyrazolone, 2-chlorophenyl-3-methyl-5-pyrazolone, 2',5'- dichloro- 3 I methyl 5 pyrazolone, 1-(3 -'sulfonamidophenyl)-3-methyl-5-pyrazolone, dimethyl dihydroresorcisodium .orpotassium or alkaline earth .oxidesand,

In addition, heterocyclic.

3 nol, barbituric acid, N-methyloxindole, 1,3,3-trimethyl-2- methylene-indoline, S-methoxy-1,3,3-trimethyl-2-methylene-indoline, phenyl acetonitrile, p-chlorophenylacetonitrile, p-cyanophenylacetonitrile, etc.

The following examples will illustrate the manner in which the polymethine dyes of the present invention are prepared. It is to be clearly understood that these examples are merely illustrative and are not to be construed as being =limitative.

Example I Into a reflux flask were placed 12 grams of N-methylp,p-iminodibenzaldehyde, 13 grams of ethyl cyanoacetate, 50 ml. of isopropanol and 5 drops of piperidine. The mixture was agitated and heated under reflux for one hour. Upon cooling the bright orange solid that separated was collected and dried. The yield of the dry product was 17.5 grams, having a melting point of 1201 C. and represents a yield of 81% of the theoretical amount.

Example II Example I was repeated with the exception that 13 grams of ethyl cyanoacetate were replaced by 18 grams of 1-phenyl-3-rnethyl-S-pyrazolone. The yield of the product was 26 grams having a melting point of 139-143 C. which amounted to 95% of the theoretical amount.

Example III C OlCHzCHzC Example I was repeated with the exception that 13 grams of ethyl cyanoacetate were replaced by 16 grams of cyanoethyl cyanoacetate. The yield of the product Was 26.5 grams having a melting point of 134-6" C. which amounted to 99+% of the theoretical amount.

Example IV 12 grams N-methylimino-bis-benzaldehyde, 13 grams benzyl cyanide (phenyl acetonitrile), 50 cc. methanol and 0.0l gram sodium rnethoxide were refluxed for 4 hours, cooled and the product filtered. It was a tan solid melting at 131-142 C.

Example V C'HzCHn HsCzOzC 14.7 grams N,N-di- (p,p'-di-formylphenyl)piperazine, 24.0 grams ethyl cyanoacetate, 100 cc. isopropanol and 5 drops of piperidine were refluxed 3 hours. The solution COzGzHl was cooled and the precipitate was collected. It had a brownish appearance, weighed 19 grams and melted above W Q Q Example VII a Oon=c 0 SO CH1 2 12 grams N-methylimino-bis-benzaldehyde, 20 grams cyanomethyl p-tolyl sulfone, 50 cc. isopropanol, and 5 drops of piperidine were refluxed for 30 minutes. The mixture was cooled and the solid collected. Upon recrystallization from ethanol, there was obtained 16 grams of prodnot (54%) melting at 140-4 C.

Example VIII 11 grams tri-(p,p',p"-formylphenyl)amine, 11 grams ethyl cyanoacetate, 50 cc. ethanol and 5 drops of piperidine were refluxed for one hour. The mixture was cooled and 5.3 grams (30%) of product was isolated. It melted at 148-160 C.

Example IX 6.6 grams tri-(p,p,p"-formylphenyl)amine, 10.8 grams 3-methyl-l-phenyl-S-pyrazolone, 25 cc. ethanol and 5 drops of piperidine were heated at reflux for 30 minutes. On cooling, an oil separated. This later solidified to give 15.5 grams (96%) of a material melting at 172l80 C.

While we have disclosed the preferred embodiments of our invention, it will be readily apparent to those skilled in the art that many changes may be made in the process ing steps disclosed above without departing from the spirit thereof. The scope of the invention is to be limited solely by the appended claims. 7

We claim: 1. Polymethine dyestufis selected from the class con- 0 sisting of the following formulae:

ra in it.

3. A polymethine dyestutf having the following for- R: GE -C R, CHQN CH=CFCH: wherein R represents a member selected from the class 5 O=(l3\ consisting of lower alkyl, phenyl, N

and 4. A polymethine dyestutf having the following formula:

COICHIOHBCN 5. A polymethine dyestufi having the following for- 2o mula: R1 represents a member selected from the class consisting 0 of acetyl, cyano and carbalkoxy groups in which the OH'N Q alkyl of the carbalkoxy group is a lower alkyl group, R2 represents a member selected from the class consisting 2 of acetyl, carbamide, carbalkoxy, dialkyl carbamide and N-hydroxy alkyl carbamide groups in which the alkyl is Polymethme dyesmfi havlng the ollowing fora lower alkyl group, carbochloroethoxy, carbohydroxymula' ethoxy, cyanocarbethox p-tolylsulfone, benzyl, and tetrahydrofurfuryl groups, R3 represents a member selected 0HrN GH=O 0 from the class consisting of methyl, carboxy and carboethoxy groups, and R4 represents a member selected from the class consisting of hydrogen, phenyl, chlorophenyl 2 and sulfonamidophenyl groups.

2. A polymethine dyestutf having the following for- References Cited m the file of fins patent mula: UNITED STATES PATENTS 2,028,141 Ackerman Ian. 21, 1936 N/ 2,431,370 Wilson Mar. s, 1948 CH 2,465,412 Wilson Mar. 29, 1949 2,558,285 Wilson June 26, 1951 

1. POLYMETHINE DYESTUFFS SELECTED FROM THE CLASS CONSISTING OF THE FOLLOWING FORMULAE: 